U.S. patent application number 15/507446 was filed with the patent office on 2017-10-05 for aqueous coating materials.
This patent application is currently assigned to Wacker Chemie AG. The applicant listed for this patent is Wacker Chemie AG. Invention is credited to Albert HAUSBERGER, Frank SANDMEYER, Martin SEBALD.
Application Number | 20170283654 15/507446 |
Document ID | / |
Family ID | 56409612 |
Filed Date | 2017-10-05 |
United States Patent
Application |
20170283654 |
Kind Code |
A1 |
SANDMEYER; Frank ; et
al. |
October 5, 2017 |
AQUEOUS COATING MATERIALS
Abstract
Silicone resin dispersions containing at least one silicone
resin having at least two differently substituted T units are used
in aqueous coating materials producible therefrom for mineral
building materials, wood or metal. The aqueous coating materials
exhibit good hydrophobicity without beading, low water
permeability, and acquire these properties rapidly after
application.
Inventors: |
SANDMEYER; Frank;
(Burgkirchen, DE) ; HAUSBERGER; Albert; (Kienberg,
DE) ; SEBALD; Martin; (Haiming, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Wacker Chemie AG |
Munich |
|
DE |
|
|
Assignee: |
Wacker Chemie AG
Munich
DE
|
Family ID: |
56409612 |
Appl. No.: |
15/507446 |
Filed: |
July 13, 2016 |
PCT Filed: |
July 13, 2016 |
PCT NO: |
PCT/EP2016/066593 |
371 Date: |
February 28, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C04B 41/4961 20130101;
C09D 7/20 20180101; C08G 77/70 20130101; C04B 41/4961 20130101;
C09D 183/04 20130101; C04B 2103/40 20130101; C04B 41/502
20130101 |
International
Class: |
C09D 183/04 20060101
C09D183/04; C09D 7/00 20060101 C09D007/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 30, 2015 |
DE |
10 2015 214 501.8 |
Claims
1.-9. (canceled)
10. An aqueous silicone resin dispersion, comprising (A) 10-70 wt %
of at least one silicone resin liquid at room temperature
(25.degree. C.), comprising at least 50% of repeating units of the
formula (1) R.sup.1(R.sup.2O).sub.bSiO.sub.(3-b/2) (1) where
R.sup.1 each independently are C1-C20 hydrocarbyl radicals which
carry no or one or more heteroatoms, R.sup.2 each independently are
C1-C6 hydrocarbyl radicals or a hydrogen radical, and b has a value
of 0, 1 or 2, and 0 to at most 50% of repeating units of the
formula (2), R.sup.8.sub.c(R.sup.2O).sub.dSiO.sub.(4-c-d/2) (2),
where R.sup.8 each independently at each occurrence are C1-C20
hydrocarbyl radicals, R.sup.2 has the definition stated above, c is
0, 2 or 3, d is 0, 1, 2 or 3, with the proviso that c+d.ltoreq.3,
wherein the silicone resins comprise at least 2 repeating units of
the formula (1), which are different from one another, in a ratio
of 1:100 to 100:1, and which carry at least 2 radicals R.sup.1
which are different from one another and which differ from one
another in their length or size by at least one hydrocarbon unit,
5% to 35% of all silicon-bonded substituents in formula (1) are of
the subformula (R.sup.2O) in which R.sup.2 is a C1-C6 hydrocarbyl
radical, at most 5% of all silicon-bonded substituents in formula
(1) are of the subformula (R.sup.2O) in which R.sup.2 is a hydrogen
radical, in at least 5% of all the repeating units of the formula
(1), b=0, in at least 5% of all the repeating units of the formula
(1), b=1, and in at most 25% of all the repeating units of the
formula (1), b=2 B) 0-2 wt % of one or more organopolysiloxanes
comprising SiC-bonded radicals with basic nitrogen, with the
proviso that the amine number of the organopolysiloxanes with basic
nitrogen is at least 0.01, (C) 0.1-30 wt % of at least one
dispersing assistant, (D) 10-70 wt % of water, (E) 0.01-10 wt % of
at least one auxiliary, and (F) 0 to 6 wt % of at least one
alkylalkoxysilane whose alkyl radicals are C1-C20 alkyl radicals
and whose alkoxy groups consist of oxygen-bonded C1-C6 alkyl
radicals.
11. The aqueous silicone resin dispersion of claim 10, wherein
R.sup.1 is selected from C1-C20 alkyl radicals without heteroatoms,
and aryl radicals.
12. The aqueous silicone resin dispersion of claim 10, wherein
R.sup.1 is selected from C1-C20 alkyl radicals without
heteroatoms.
13. The aqueous silicone resin dispersion of claim 10, wherein
R.sup.1 is selected from the group consisting of methyl, ethyl,
n-octyl, isooctyl radicals, and mixtures thereof.
14. The aqueous silicone resin dispersion of claim 10, wherein
R.sup.1 are methyl and isooctyl radicals.
15. The aqueous silicone resin dispersion of claim 10, wherein
R.sup.1 is selected such that there is a combination of at least
one C1-C20 alkyl radical without heteroatoms with at least one aryl
radical.
16. The aqueous silicone resin dispersion of claim 10, wherein
R.sup.1 are methyl and phenyl radicals.
17. Aqueous coating materials, comprising at least one silicone
resin dispersion of claim 10.
18. The aqueous coating materials of claim 17, which is a paint,
stain, varnish or render.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is the U.S. National Phase of PCT Appln.
No. PCT/EP2016/066593 filed Jul. 13, 2016, which claims priority to
German Application No. 10 2015 214 501.8 filed Jul. 30, 2015, the
disclosures of which are incorporated in their entirety by
reference herein.
BACKGROUND OF THE INVENTION
1. Field of the Invention
[0002] The invention relates to silicone resin dispersions
comprising at least one silicone resin having at least two
differently substituted T units and to aqueous coating materials
producible therefrom for mineral building materials, wood or
metal.
2. Description of the Related Art
[0003] Protection of building materials from the damaging effect of
water is critically important to long-term preservation of the
performance capacity and hence the perennial integrity of a
building material. Reflecting this importance, there are numerous
methods by which building materials are protected from water.
Within the family of these protective measures, a particularly
prominent position is occupied by coating systems and impregnation
systems, since they are simple to apply and therefore offer
particular advantages to the user. Coatings, moreover, are required
to be environmentally friendly and sustainable, thus being free
from toxicologically objectionable or eco-unfriendly substances.
They are required to possess good substrate adhesion and good
cohesive qualities. Furthermore, they are to be permeable to water
vapour while at the same time effectively blocking the passage of
liquid water. Construction coatings, furthermore, must themselves
be long-lived and aesthetically appealing.
[0004] For achieving this profile of properties, the use of
silicone resins as binders or co-binders in construction paints has
often been proposed.
[0005] EP1034209B1 teaches the use of aqueous silicone resin
dispersions as construction coating compositions. The active
ingredient in the silicone resin dispersions comprises silicone
resins which are composed primarily of T units and which may also
include M, D and Q units. They are hydroxy-functional, necessarily
containing at least 0.05 wt % of hydroxyl groups. The dispersions
further comprise other components serving, among other purposes,
for curing and emulsification of the resin. The silicone resin
dispersions of the invention are used for the formulation of
water-repellent construction paints.
[0006] U.S. Pat. No. 5,316,799 describes a hydrophobic impregnating
composition which comprises a silane or linear siloxane and which
is employed as a mixture with a paint. The system as a whole is
water-repellent and hence superficially hydrophobic.
[0007] EP0606671A1 describes organopolysiloxane resin-, filler- and
alkoxysilane- and optionally alkoxysiloxane-containing emulsions
which are applied to mineral building materials for the purpose of
hydrophobilizing them. The silicone resins are MQ or MDQ resins.
The fillers have a specific surface area of at least 40 m.sup.2/g
and are added in small quantities.
[0008] EP0616989A1 teaches a hydrophobizing agent as an aqueous
impregnating emulsion for mineral building materials, comprising a
mixture of alkylalkoxysilanes and alkylalkoxysiloxanes in a mixing
ratio of 0.5:1 to 0.98:1. The alkylalkoxysilanes are substituted by
alkyl radicals of different lengths. The alkylalkoxysiloxanes are
composed of alkyl-substituted T and D units. Different alkyl
substituents are allowed on the respective silicone units. In view
of the inaccurate disclosure of the alkylalkoxysiloxane unit, its
structure is not clearly apparent, but the information provided
does suggest that the T units have alkyl substituents more than 3 C
atoms in length and the D units may be substituted with mixtures of
short-chain and long-chain alkyl radicals. There is no evidence of
two T units with different alkyl substitution. Included in the
mixture in accordance with the invention are alkyltrialkoxysilanes,
and so in principle there are two differently substituted silicon
species in the mixture, each surrounded by three oxygen atoms and
carrying different alkyl radicals. The presentation form, however,
is not a homogeneous molecule in which these two units are united
with one another by chemical combination, but is instead a mixture
of the two different silicon species. The aqueous impregnating
emulsion of the invention that is obtained produces a water barrier
effect by development of surface-hydrophobicity.
[0009] EP1844120B1 teaches high-viscosity aqueous emulsions as
hydrophobizing agents for mineral building materials, containing
50%-90% of functional alkoxysilanes and/or their oligomers and/or
organoalkoxysiloxanes. If the functional alkoxysilanes are
alkyl-substituted, the alkyl radicals comprise at least 3 C atoms.
The organoalkoxysilanes are linear siloxanes which may contain an
Si--C-bonded radical, it being possible in principle for there to
be differently alkyl- or aralkyl-substituted silicon atoms. On each
silicon atom on the chain, moreover, there is an alkoxy group, with
two such groups being bonded at each of the chain ends. As a result
of this substitution pattern, a chain structure composed
exclusively of D units is formed. Accordingly, the
organoalkoxysiloxanes have a very high alkoxy functionality. There
is no limit on the viscosity of the high-viscosity emulsions, but
the use examples show that the systems in question are paste-like.
The emulsions described have a superficial hydrophobizing
effect.
[0010] EP0098940A2 teaches aqueous preparations comprising
polyorganosiloxane compounds. The polyorganosiloxanes are
alkoxy-rich partial hydrolysates optionally of different
alkoxysilanes, it being possible for the silicon atoms to be
substituted by different Si--C-bonded alkyl radicals or aralkyl
radicals and/or mixtures thereof. The aqueous preparations are
prepared by adding an aqueous preparation of polyvinyl alcohol to
the partial silane hydrolysate and then subjecting the system to
strong acidification. Under these conditions, the partial
hydrolysates undergo further hydrolysis and condensation and, in so
doing, form considerable quantities of alcohol, which are included
in the end product. As a result, aqueous preparations with possibly
critical flash points are produced, which inevitably contain
alcohols, which may possibly be toxic, in the form of methanol, for
example. The siloxane condensates are poorly defined. Accordingly,
EP0098940 also gives no information on the composition of the
siloxane condensates after the production of the aqueous
preparations. The aqueous preparations are said to be stable, but
to the skilled person it is clear that a criterion for the
stability of such a preparation is the formation of alcohol during
the storage period. Since alcohols in unknown quantity are produced
during the production process itself, the stability concept here is
incomprehensible and arbitrary. Coating materials are given as a
possible application of the aqueous preparations; in view of the
inherent toxicological, safety-related and environmental
disadvantages, the suitability of the aqueous preparations of the
invention is highly questionable, if not completely out of the
question.
[0011] EP0287085 relates to hydrophobizing, aqueous,
silicon-containing coating systems which comprise as their binder a
mixture of organopolysiloxane and ethylene-vinyl chloride
copolymers. Example 1 describes one such hydrophobizing silicone
resin paint, which comprises a silicone resin containing not only
methyl groups but also isooctyl groups as Si--C-bonded radicals on
monoalkylsiloxane units. Since the rest of the substitution pattern
is not disclosed, all that can be inferred is that these are units
which possess only one silicon-bonded alkyl group. All that is
otherwise disclosed regarding this organopolysiloxane is that there
is a hydrophobizing aqueous coating material.
[0012] In the prior art outlined above, the silicone components are
always used in order to bring about hydrophobic properties, more
particularly superficial hydrophobic properties, which are commonly
manifested in a beading effect. Tests of this kind are occasionally
employed for verification of the hydrophobicity claimed. This means
that water is unable to wet the surface, instead concentrating into
droplets. It is common knowledge and easily understood that a
compact droplet evaporates more slowly than a film of the same
amount of water present in a form spread uniformly over a
relatively large area. As a result, while the pronounced
hydrophobicity of the silicone components does prevent the passage
of water through a coating or impregnation, the surface remains
moist for longer at those areas at which the water collects in
droplets, and thus offers a relatively easy point of attack for
microorganisms which are able to utilize the locations of increased
moisture for their growth. In this way, pronounced hydrophobicity
leads to an increased risk of microorganism infestation at
locations where the evaporation of the moisture from the surface is
not promoted by particularly advantageous conditions such as wind
and heat, and results, therefore, in damage to the surface and to
loss of its protective and of its aesthetic qualities.
[0013] Nevertheless, an extremely positive property of the
hydrophobicity is to prevent the passage of liquid water through
the respective coating, so that the underlying substrate remains
dry and thus retains its performance capacity over the long term.
This applies not only to mineral substrates but also to wood and
metal. In the case of the latter, the water barrier effect makes a
key contribution to preventing corrosion. A combination of a fairly
hydrophilic surface yet with good water blocking effect on the part
of the coating would be ideal--in other words, moisture management
rather than simple hydrophobicity. Since such properties are
mutually exclusive, it is not obvious that they can be achieved
with one product and, in particular, by an application of only one
kind of coating material. The expectation would instead be of such
a combination of at least two-coat application using different
coating materials, with each one taking on one of the two
functions, water barrier effect and surface hydrophilicity.
[0014] Furthermore, the applications cited above refer to the slow
curing of the silicone resins, and in some cases recommend
catalysts and activators to accelerate this curing, such as in
EP1034209B1. During the cure time of the siloxane components, the
silicone does not exhibit its full performance capacity in respect
either of mechanical qualities or of water barrier effect.
[0015] Another disadvantage of the siloxane dispersions from the
prior art is the fact that the emulsifiers which are needed in
order to maintain the silicone stably in the aqueous phase remain
in the paint following its application and, on account of their
hydrophilicity, reduce the water barrier effect of the paint in the
period immediately following application of the paint. Only after
the emulsifiers have been washed out do such paints attain their
full water barrier effect.
SUMMARY OF THE INVENTION
[0016] It was an object of the present invention, therefore, to
provide aqueous siloxane dispersions which do not have the
abovementioned disadvantages--in other words, dispersions which,
not least immediately after paint application, display the full
water barrier effect of the paint, and also the full mechanical
performance, with the overall level of the performance capacity of
the paint fully conforming to the other requirements. The siloxane
dispersions here are to result in coating materials which do not
have a hydrophobic surface, but instead allow water to spread out
to an extremely thin film and thus which promote its rapid
evaporation, in order to keep the surface sustainably dry. In other
words, they are in no way to result in a beading effect. At the
same time, they are to prevent effectively the passage of water
through the coating material film, and are to provide all of these
properties after just a single coat application through the use of
only one kind of coating material.
[0017] Surprisingly it has been found that certain silicone resins
in the form of aqueous siloxane dispersions achieve this object.
This is especially surprising on account of the fact that similar
silicone resins are already known in the prior art, but all have
consistently hydrophobic properties and result correspondingly in
hydrophobic coating materials. The silicone resins of the invention
and dispersions thereof are therefore a specific selection of
silicone resins which run counter to those in the prior art and
exhibit entirely unexpected properties.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0018] In the present text, substances are characterized by
reporting of data obtained by means of instrumental analysis. The
measurements involved either are carried out in accordance with
publicly available standards, or are determined according to
specially developed methods. In order to ensure that the teaching
given is clear, the methods used are reported here:
Viscosity:
[0019] Unless otherwise reported, the viscosities are determined by
rotational-viscosimetric measurement in accordance with DIN EN ISO
3219. Unless otherwise reported, all viscosity reports are valid at
25.degree. C. and atmospheric pressure of 1013 mbar.
Refractive Index:
[0020] The refractive indices are determined in the wavelength
range of visible light--unless otherwise reported, at 589 nm at
25.degree. C. under atmospheric pressure of 1013 mbar in accordance
with standard DIN 51423.
Transmission:
[0021] The transmission is determined by UV VIS spectroscopy. An
example of a suitable instrument is the Jena Specord 200 analytical
system.
[0022] The measurement parameters used are as follows: range:
190-1100 nm,
[0023] step length: 0.2 nm, integration time: 0.04 s, measurement
mode: step operation. First there is a reference measurement
(background). A quartz plate mounted on a sample holder (quartz
plate dimensions: H.times.W approx. 6.times.7 cm, thickness approx.
2.3 mm) is inserted into the sample beam path and measured against
air.
[0024] This is followed by the sample measurement. A quartz plate
mounted on the sample holder and with sample applied--layer
thickness of applied sample approx. 1 mm--is placed into the sample
beam path and measured against air. Internal computation relative
to background spectrum yields the transmission spectrum of the
sample.
Molecular Compositions:
[0025] The molecular compositions are determined by means of
nuclear magnetic resonance spectroscopy (regarding the terminology
see ASTM E 386: High-resolution nuclear magnetic resonance
spectroscopy (NMR): Terms and symbols), with measurement of the
.sup.1H nucleus and of the .sup.29Si nucleus.
Description of .sup.1H NMR Measurement
[0026] Solvent: CDCl.sub.3, 99.8% d
[0027] Sample concentration: about 50 mg/l ml CDCl.sub.3 in 5 mm
NMR vial
[0028] Measurement without addition of TMS, spectral referencing of
residual CHCl.sub.3 in CDCl.sub.3 at 7.24 ppm
[0029] Spectrometer: Bruker Avance I 500 or Bruker Avance HD
500
[0030] Probe head: 5 mm BBO probe head or SMART probe head (from
Bruker)
Measuring Parameters:
[0031] Pulprog=zg30
[0032] TD=64 k
[0033] NS=64 or 128 (depending on the sensitivity of the probe
head)
[0034] SW=20.6 ppm
[0035] AQ=3.17 s
[0036] D1=5 s
[0037] SFO1=500.13 MHz
[0038] O1=6.175 ppm
Processing Parameters:
[0039] SI=32 k
[0040] WDW=EM
[0041] LB=0.3 Hz
[0042] Depending on the type of spectrometer used, individual
adjustments of the measurement parameters may be required.
Description of .sup.29Si NMR Measurement
[0043] Solvent: C.sub.6D.sub.6 99.8% d/CCl.sub.4 1:1 v/v with 1 wt
% Cr(acac).sub.3 as relaxation reagent [0044] Sample concentration:
about 2 g/1.5 ml solvent in 10 mm NMR vial [0045] Spectrometer:
Bruker Avance 300 [0046] Probe head: 10 mm 1H/13C/15N/29Si
glass-free QNP probe head (from Bruker)
Measuring Parameters:
[0047] Pulprog=zgig60
[0048] TD=64 k
[0049] NS=1024 (depending on the sensitivity of the probe head)
[0050] SW=200 ppm
[0051] AQ=2.75 s
[0052] D1=4 s
[0053] SFO1=300.13 MHz
[0054] O1=-50 ppm
Processing Parameters:
[0055] SI=64 k
[0056] WDW=EM
[0057] LB=0.3 Hz
[0058] Depending on the type of spectrometer used, individual
adjustments of the measurement parameters may be required.
Molecular Weight Distributions:
[0059] Molecular weight distributions are determined as weight
averages Mw and as number averages Mn, using the method of gel
permeation chromatography (GPC or size exclusion chromatography
(SEC)) with polystyrene standard and refractive index (RI)
detector. Unless otherwise noted, THF is used as mobile phase and
DIN 55672-1 applies. The polydispersity is the Mw/Mn quotient.
Glass Transition Temperatures:
[0060] The glass transition temperature is determined according to
differential scanning calorimetry (DSC) according to DIN 53765,
perforated crucible, heating rate 10 K/min.
[0061] The invention thus pertains to aqueous silicone resin
dispersions comprising
[0062] (A) 10-70 wt % of at least one silicone resin liquid at room
temperature (25.degree. C.), the liquid silicone resin [0063]
comprising at least 50% of repeating units of the formula (1)
[0063] R.sup.1(R.sup.2O).sub.bSiO.sub.(3-b/2) (1) [0064] where
[0065] R.sup.1 denotes C1-C20 hydrocarbyl radicals which carry no
or at least one heteroatom, [0066] R.sup.2 denotes C1-C6
hydrocarbyl radicals or a hydrogen radical, and [0067] b has a
value of 0, 1 or 2, [0068] and 0 to at most 50% of repeating units
of the formula (2),
[0068] R.sup.8.sub.c(R.sup.2O).sub.dSiO.sub.(4-c-d/2) (2), [0069]
where [0070] R.sup.8 independently at each occurrence denotes
C1-C20 hydrocarbyl radicals, [0071] R.sup.2 has the definition
stated above, [0072] c may be 0, 2 or 3, [0073] d may be 0, 1, 2 or
3, [0074] with the proviso that c+d 3, [0075] characterized in that
[0076] the silicone resins comprise at least 2 repeating units of
the formula (1), which are different from one another, in a ratio
of 1:100 to 100:1, and which carry at least 2 radicals R.sup.1
which are different from one another and which differ from one
another in their length or size by at least one hydrocarbon unit,
[0077] 5% to 35% of all silicon-bonded substituents in formula (1)
are of the subformula (R.sup.2O) in which R.sup.2 is a C1-C6
hydrocarbyl radical, [0078] at most 5% of all silicon-bonded
substituents in formula (1) are of the subformula (R.sup.2O) in
which R.sup.2 is a hydrogen radical, [0079] in at least 5% of all
the repeating units of the formula (1), b=0, [0080] in at least 5%
of all the repeating units of the formula (1), b=1, [0081] in at
most 25% of all the repeating units of the formula (1), b=2
[0082] B) 0-2 wt % of at least one organopolysiloxane comprising
SiC-bonded radicals with basic nitrogen, with the proviso that its
amine number is at least 0.01,
[0083] (C) 0.1-30 wt % of at least one dispersing assistant,
[0084] (D) 10-70 wt % of water,
[0085] (E) 0.01-10 wt % of at least one auxiliary, and
[0086] (F) 0 to 6 wt % of at least one alkylalkoxysilane whose
alkyl radicals are C1-C20 alkyl radicals and whose alkoxy groups
consist of oxygen-bonded C1-C6 alkyl radicals.
[0087] The silicone resin dispersion preferably possesses a
viscosity of between 10 and 50,000 mPas, more preferably 20-10,000
mPas, and most preferably 20-5000 mPas at 25.degree. C.
[0088] Through appropriate selection of the preparation components
and their relative amounts, the silicone resin dispersions of the
invention can also be formulated in such a way that they result,
rather than liquid emulsions, in paste-like aqueous preparations
which have the form of a cream and possess viscosities of more than
100,000 mPas at 25.degree. C.
[0089] The silicone resin dispersions of the invention are produced
by the known, prior-art methods. From the silicone resin
dispersions of the invention, by methods according to the prior
art, aqueous coating materials of the invention are likewise
obtained. The aqueous coating materials of the invention are
produced by known methods from the prior art, with the
characteristic feature that at least one silicone resin dispersion
of the invention is admixed.
[0090] In a method for coating and for obtaining the advantageous
properties of the coating materials of the invention on mineral
building materials, wood or metal, the aqueous coating material of
the invention is applied to mineral building materials, wood or
metal.
[0091] The most important coating materials of the invention are
paints, stains, varnishes and renders and are applied to mineral
building materials, wood or metal. A particular characteristic of
the silicone resin dispersions of the invention is that they
produce aqueous coating materials for mineral building materials,
wood or metal, characterized in that the water barrier effect of
the coating materials even without the emulsifiers having been
washed out attains a value in class 3 according to DIN EN 1062-3
(<0.1 kg/m.sup.2 h.sup.0.5). The mechanical strength tested
according to DIN 53778-2 4 days after application attains a value
of >10,000 abrasion cycles.
[0092] Moreover, no beading effect is obtained, indicating surface
hydrophobicity, but instead a water droplet which is placed onto
the surface spreads over that surface, but without entering into or
passing through the paint coat. Accordingly, the coating materials
of the invention produce coatings which at the same time allow
water to spread on the surface and have a pronounced water barrier
effect. The aqueous coating materials are preferably paints and
stains, more particularly paints.
[0093] The coating materials suitable for the purposes of the
invention are either supplied in dry form, but applied in the form
of a water-containing preparation, such as powder paints and
pulverulent dry renders, or are wet, such as paste-like,
water-containing paints, examples being silicone resin paints,
silicate paints and emulsion paints, or such as paste-like,
water-containing renders, examples being synthetic resin renders
and silicone resin renders.
[0094] The impregnating coating compositions suitable for the
purposes of the invention can be classified according to
application thickness, and are applied thickly, such as renders in
the millimetre to centimetre range, or are applied thinly, such as
hiding paints and varnishes in the 100 .mu.m to 1 millimetre range,
or translucently to hidingly such as impregnating materials and
low-build and high-build stains in the 3 .mu.m to 100 .mu.m
range.
[0095] The impregnating coating materials suitable for the purposes
of the invention may be used both inside and out, preferably
outdoors. Examples of coating materials of the invention used on
buildings are silicate renders, dry renders, brush-applied fillers,
reinforcing compounds, filling compounds, synthetic resin renders,
mineral renders, silicone resin renders and synthetic resin-bound
coatings. Preferred examples are interior paints, masonry paints,
mineral paints, emulsion paints, silicone resin paints, silicone
masonry paints, stains, varnishes, silicate emulsion paints,
silicate paints, lime paints, and lime emulsion paints.
Silicone Resins (A)
[0096] Examples of hydrocarbyl radicals R.sup.1 are alkyl radicals,
particularly C1-C3-alkyl radicals, and also C2-C20 alkyl radicals,
and alkenyl radicals such as the vinyl, allyl, n-5-hexenyl,
4-vinylcyclohexyl and the 3-norbornenyl radical; aryl radicals such
as the phenyl-, biphenylyl, naphthyl and anthryl and phenanthryl
radical; alkaryl radicals such as o-, m- and p-tolyl radicals,
xylyl radicals and ethylphenyl radicals; aralkyl radicals such as
the benzyl radical, and the alpha- and the beta-phenylethyl
radicals. Particularly preferred are the C1-C20-alkyl radicals and
aryl radicals, not substituted by heteroatoms. In particular,
C1-C16 alkyl radicals without heteroatoms, particularly the methyl,
the ethyl, the n-octyl and the isooctyl radical.
[0097] The ratio of the two different repeating units (1) to one
another is 1:100 to 100:1, preferably 1:99-99:1, more preferably
1:97 to 97:1, more particularly 1:96 to 96:1.
[0098] It is preferred, and has proved to be particularly
advantageous, if the repeating unit (1) having the more carbon-rich
substituent is present at not more than 75 mol % of all the
repeating units of the formula (1). Conversely this means that the
repeating unit (1) having the less carbon-rich substituent is
present at not less than 25 mol % of all the repeating units of the
formula (1). In one particularly preferred embodiment of the
invention, the repeating units of the formula (1) having the less
carbon-rich substituent are present in the majority, i.e. more than
50 mol % of all the repeating units of the formula (1).
[0099] Examples of particularly preferred combinations of radicals
R.sup.1 are such that R.sup.1 is selected such that at least one
C1-C20 alkyl radical without heteroatoms is combined with at least
one aryl radical, such as phenyl and methyl radicals, phenyl and
ethyl radicals, isooctyl and phenyl radicals, and n-octyl and
phenyl radicals. Further preferred combinations of two different
C1-C16 alkyl radicals without heteroatoms are the n-butyl radical
and the ethyl radical, the n-butyl radical and the methyl radical,
the ethyl radical and the methyl radical, the n-octyl radical and
the methyl radical, the isooctyl radical and the methyl radical,
the n-octyl radical and the ethyl radical, the isooctyl radical and
the ethyl radical, wherein the combination of phenyl radical and
methyl radical, ethyl radical and methyl radical, isooctyl radical
and methyl radical, ethyl radical and isooctyl radical, and phenyl
radical and isooctyl radical, are particularly advantageous. A
combination of methyl and isooctyl radicals and of methyl and
phenyl radicals as the two different radicals R.sup.1 has proved to
be particularly effective. In the case of the combination of
isooctyl radical and methyl radical, there are preferably more
repeating units of the formula (1) that carry methyl radicals than
those that carry isooctyl radicals. The ratio of the number of
repeating units of the formula (1) which carry methyl radicals to
the number of repeating units of the formula (1) which carry
isooctyl radicals is preferably 51:49 to 99:1, more preferably
55:45 to 98:2, more particularly 60:40 to 98:2. Ratios of 60:40,
70:30, 90:10 and 95:5 have proved to be particularly effective.
[0100] In the case of the combination of phenyl radicals and methyl
radicals, the following ratios of the number of repeating units of
the formula (1) which carry methyl radicals to the number of
repeating units of the formula (1) which carry phenyl radicals are
particularly preferred: 98:2 to 10:90, more preferably 98:2 to
20:80, more particularly 98:2 to 30:70. Ratios which have proved to
be particularly advantageous are those in the ranges 98:2-70:30 and
25:75-40:60, especially 97:3, 95:5, 90:10, 70:30, 35:65 and
45:55.
[0101] Also possible and in accordance with the invention is the
combination of more than two different radicals. In that case, the
preferred ratios specified above for the combination of two
different radicals are valid mutatis mutandis if the more
carbon-richly substituted repeating units are added together and
made into a ratio relative to the repeating unit which carries the
smallest and/or the least carbon-rich substituent; in the manner
described above, a distinction is made between combinations
involving aromatic substituents and those not involving aromatic
constituents. In the case where there are more than two different
repeating units of the formula (1), as well, preferred combinations
are those of methyl, ethyl, phenyl, n-butyl, n-octyl, isooctyl,
more particularly of methyl, ethyl, phenyl and isooctyl, especially
of methyl, phenyl and isooctyl.
[0102] Examples of the radicals R.sup.2 are the methyl, ethyl,
n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl radicals;
pentyl radicals such as the n-pentyl radical, and hexyl radicals,
such as the n-hexyl radical; the ethyl radicals are particularly
preferred.
[0103] Preferably (A) is present in the silicone resin dispersion
at from 10 to 65 wt %, more preferably from 25 to 60 wt %.
Organopolysiloxanes (B)
[0104] The organopolysiloxanes (B) are preferably those composed of
units of the general formula (4)
R.sup.3.sub.a*R.sup.4.sub.b*(OR.sup.5).sub.c*SiO.sub.(4-a*-b*-c*)/2
(4)
[0105] in which [0106] R.sup.3 denotes identical or different
monovalent, halogen-substituted or non-halogen-substituted,
SiC-bonded C.sub.1-C.sub.20 hydrocarbyl radicals which are free of
basic nitrogen, [0107] R.sup.4 denotes identical or different
monovalent, halogen-substituted or non-halogen-substituted,
SiC-bonded C.sub.1-C.sub.30 hydrocarbyl radicals containing basic
nitrogen, [0108] R.sup.5 identically or differently is a hydrogen
atom or C.sub.1-C.sub.6 alkyl radicals, [0109] a* is 0, 1, 2 or 3,
[0110] b* is 0, 1, 2 or 3, on average at least 0.05, and [0111] c*
is 0, 1, 2 or 3, with the proviso that the sum of a*, b* and c* is
not more than 3 and that the amine number of the organopolysiloxane
(B) is at least 0.01.
[0112] The amine number identifies the number of ml of 1N HCl
required to neutralize 1 g of organopolysiloxane (B). The amine
number of organopolysiloxane (B) is preferably at least 0.1, more
preferably at least 0.2, and preferably not more than 8, more
preferably not more than 4.
[0113] Examples and preferred examples of the radical R.sup.3 are
the examples already disclosed above for radical R.sup.1.
Particularly preferred for the radical R.sup.3 are the methyl
radical and the isooctyl radical.
[0114] The radical R.sup.4 is preferably a radical of the general
formula (3)
R.sup.6.sub.2NR.sup.7 (3)
[0115] where
[0116] R.sup.6 may be identical or different and is hydrogen or a
monovalent, substituted or unsubstituted C.sub.1-C.sub.10
hydrocarbyl radical or C.sub.1-C.sub.10 aminohydrocarbyl radical
and
[0117] R.sup.7 is a divalent C.sub.1-C.sub.15 hydrocarbyl
radical
[0118] Examples of radical R.sup.6 are the examples already
disclosed above, of hydrocarbyl radicals and also of hydrocarbyl
radicals substituted by amino groups, such as aminoalkyl radicals,
particular preference being given to the aminoethyl radical.
[0119] There is preferably at least one hydrogen atom bonded to
each nitrogen atom in the radicals of the general formula (3).
[0120] Radical R.sup.7 preferably comprises divalent hydrocarbyl
radicals having 1 to 10 carbon atoms, more preferably 1 to 4 carbon
atoms, more particularly the n-propylene radical.
[0121] Examples of radical R.sup.7 are the methylene, ethylene,
propylene, butylene, cyclohexylene, octadecylene, phenylene and
butylene radicals.
[0122] Preferred examples of radicals R.sup.4 are
[0123] H.sub.2N(CH.sub.2).sub.3--,
[0124] H.sub.2N(CH.sub.2).sub.2NH(CH.sub.2).sub.2--,
[0125] H.sub.2N(CH.sub.2).sub.2NH(CH.sub.2).sub.3--,
[0126] H.sub.2N(CH.sub.2).sub.2--,
[0127] H.sub.3CNH(CH.sub.2).sub.3--,
[0128] C.sub.2H.sub.5NH(CH.sub.2).sub.3--,
[0129] H.sub.3CNH(CH.sub.2).sub.2--,
[0130] C.sub.2H.sub.5NH(CH.sub.2).sub.2--,
[0131] H.sub.2N(CH.sub.2).sub.4--,
[0132] H.sub.2N(CH.sub.2).sub.5--,
[0133] H(NHCH.sub.2CH.sub.2).sub.3--,
[0134] C.sub.4H.sub.9NH(CH.sub.2).sub.2NH(CH.sub.2).sub.2--,
[0135] cyclo-C.sub.6H.sub.11NH(CH.sub.2).sub.3--,
[0136] cyclo-C.sub.6H.sub.11NH(CH.sub.2).sub.2--,
[0137] (CH.sub.3).sub.2N(CH.sub.2).sub.3--,
[0138] (CH.sub.3).sub.2N(CH.sub.2).sub.2--,
[0139] (C.sub.2H.sub.5).sub.2N(CH.sub.2).sub.3-- and
[0140] (C.sub.2H.sub.5).sub.2N(CH.sub.2).sub.2--.
[0141] The examples of alkyl radicals R.sup.1 are valid in full for
radical R.sup.7 as well.
[0142] Examples and preferred examples of the radical R.sup.5 are
C1-C6 radicals listed above for radical R.sup.1. Especially
preferred are the methyl and the ethyl radical.
[0143] The preferred average value for a is 0 to 2, more
particularly 0 to 1.8.
[0144] The preferred average value for b is 0.1 to 0.6, more
particularly 0.15 to 0.30.
[0145] The preferred average value for c is 0 to 0.8, more
particularly 0.01 to 0.6.
[0146] The organopolysiloxanes (B) preferably have a viscosity of 5
to 5000, more preferably of 100 to 3000 mm.sup.2/s at 25.degree.
C.
[0147] Organopolysiloxanes (B) can be prepared in a known way, for
example by equilibration and/or condensing of amino-functional
silanes with organopolysiloxanes which contain alkoxy groups and/or
hydroxyl groups and which are free of basic nitrogen.
[0148] Preferably (B) is present in the silicone resin dispersion
at 0.05-2 wt %, more preferably at 0.1-1.5 wt %.
(C) Dispersing Assistants
[0149] The aqueous silicone resin dispersion comprises dispersing
assistants (C) as identified, for example, in 2006 McCutcheon's
Emulsifiers & Detergents, North American Edition, MC Publishing
Co., Glen Rock, N.J. Particularly suitable in this context are
[0150] as anionic emulsifiers (C1): [0151] 1. Alkyl sulphates,
especially those having a chain length of 8 to 18 C atoms, alkyl
and alkaryl ether sulphates having 8 to 18 C atoms in the
hydrophobic radical and 1 to 40 ethylene oxide (EO) and/or
propylene oxide (PO) units. [0152] 2. Sulphonates, particularly
alkylsulphonates having 8 to 18 C atoms, alkylarylsulphonates
having 8 to 18 C atoms, taurides, full esters and monoesters of
sulphosuccinic acid with monohydric alcohols or alkylphenols having
4 to 15 C atoms; these alcohols or alkylphenols may optionally also
be ethoxylated with 1 to 40 EO units. [0153] 3. Alkali metal salts
and ammonium salts of carboxylic acids having 8 to 20 C atoms in
the alkyl, aryl, alkaryl or aralkyl radical. [0154] 4. Phosphoric
partial esters and their alkali metal and ammonium salts,
especially alkyl and alkaryl phosphates having 8 to 20 C atoms in
the organic radical, alkyl ether phosphates and alkaryl ether
phosphates having 8 to 20 C atoms in the alkyl or alkaryl radical,
respectively, and 1 to 40 EO units. [0155] as non-ionic emulsifiers
(C2): [0156] 5. Polyvinyl alcohol additionally having 5% to 50%,
preferably 8% to 20%, of vinyl acetate units, with a degree of
polymerization of 500 to 3000. [0157] 6. Alkyl polyglycol ethers,
preferably those having 8 to 40 EO units and alkyl radicals of 8 to
20 C atoms. [0158] 7. Alkylaryl polyglycol ethers, preferably those
having 8 to 40 EO units and 8 to 20 C atoms in the alkyl and aryl
radicals. [0159] 8. Ethylene oxide/propylene oxide (EO/PO) block
copolymers, preferably those having 8 to 40 EO and PO units. [0160]
9. Adducts of alkylamines having alkyl radicals of 8 to 22 C atoms
with ethylene oxide or propylene oxide. [0161] 10. Fatty acids
having 6 to 24 C atoms. [0162] 11. Alkylpolyglycosides of the
general formula R*O--Z.sub.o, in which R* is a linear or branched,
saturated or unsaturated alkyl radical having on average 8-24 C
atoms and Z.sub.o is an oligoglycoside residue having on average
o=1-10 hexose or pentose units or mixtures thereof. [0163] 12.
Natural substances and derivatives thereof, such as lecithin,
lanolin, saponins, cellulose; cellulose alkyl ethers and
carboxyalkylcelluloses whose alkyl groups possess in each case up
to 4 carbon atoms. [0164] 13. Linear organo(poly)siloxanes
containing polar groups, especially those having alkoxy groups with
up 24 C atoms and/or up to 40 EO and/or PO groups. [0165] as
cationic emulsifiers (C3): [0166] 14. Salts of primary, secondary
and tertiary fatty amines having 8 to 24 C atoms with acetic acid,
sulphuric acid, hydrochloric acid and phosphoric acids. [0167] 15.
Quaternary alkylammonium and alkylbenzeneammonium salts, especially
those whose alkyl groups possess 6 to 24 C atoms, more particularly
the halides, sulphates, phosphates and acetates. [0168] 16.
Alkylpyridinium, alkylimidazolinium and alkyloxazolinium salts,
especially those whose alkyl chain possesses up to 18 C atoms,
especially the halides, sulphates, phosphates and acetates. [0169]
as ampholytic emulsifiers (C4): [0170] 17. Amino acids with
long-chain substitution, such as N-alkyl-di(aminoethyl)glycine or
N-alkyl-2-aminopropionoic salts. [0171] 18. Betaines, such as
N-(3-acylamidopropyl)-N,N-dimethylammonium salts having a C8-C18
acyl radical, and alkylimidazolium betaines.
[0172] Preferred dispersing assistants are non-ionic emulsifiers
(C2), especially the adducts of alkylamines with ethylene oxide or
propylene oxide listed above under 9. the alkylpolyglycosides
listed above under 11. and the polyvinyl alcohol listed above under
5. Particularly preferred polyvinyl alcohols also contain 5% to
20%, more particularly 10% to 15%, of vinyl acetate units and
preferably have a degree of polymerization of 500 to 3000, more
particularly of 1200 to 2000.
[0173] The fraction of the dispersing assistant (C) is preferably 1
to 30 wt %, more preferably 2 to 10 wt %, based on the total amount
of silicone resin dispersion.
Water (D)
[0174] The aqueous silicone resin dispersions of the invention
further comprise water (D), preferably at 10 to 70 wt %, more
preferably 15 to 60 wt %, based on the total amount of silicone
resin dispersion.
Auxiliaries (E)
[0175] As auxiliaries (E) it is possible to use all auxiliaries
which are useful, such as, for example, emulsifiers for the
homogeneous, stable dispersing of the silicone resin preparation in
water. Further auxiliaries are, for example, silicone resins which
differ from (A) or polyorganosiloxanes which differ from (B),
silanes which differ from (F), organic solvents, wetting
assistants, film-forming assistants, antifoams, adhesion promoters,
flow control agents, crosslinking catalysts, pH modifiers,
preservatives and solubilizers.
[0176] The fraction of the auxiliaries (E) is preferably 0.1 to 10
wt %, more particularly 0.1 to 8 wt %, based on the total amount of
the silicone resin dispersion.
Alkylalkoxysilane (F) The C.sub.1-C.sub.20 alkyl-C1-C6
alkoxysilanes (F) preferably possess 1 or 2 identical or different,
optionally halogen-substituted, SiC-bonded, monovalent
C.sub.1-C.sub.20 alkyl radicals, and the remaining radicals are
identical or different to C1-C6 alkoxy radicals, especially C.sub.2
or C.sub.3 alkoxy radicals. Particularly preferred are the
alkyltrialkoxysilanes, such as octyltriethoxysilane and
butyltriethoxysilane.
[0177] Examples of C.sub.2-C.sub.3 alkoxy radicals are the ethoxy,
n-propoxy, and isopropoxy radicals. Ethoxy radicals are
particularly preferred.
[0178] Methoxysilanes hydrolyse too quickly for many applications
and have less storage stability than longer alkoxy radicals. For
many applications, C.sub.4-C.sub.6 alkoxy radicals are too sluggish
in reaction.
[0179] Examples of the C.sub.1-C.sub.20 alkyl radicals in (F) are
the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
tert-butyl, n-pentyl, isopentyl, neopentyl, and tert-pentyl
radicals; hexyl radicals such as the n-hexyl radical; heptyl
radicals such as the n-heptyl radical; octyl radicals such as the
n-octyl radical and isooctyl radicals such as the
2,2,4-trimethylpentyl radical; nonyl radicals such as the n-nonyl
radical; decyl radicals such as the n-decyl radical and dodecyl
radicals, such as the n-dodecyl radical; cycloalkyl radicals such
as cyclopentyl, cyclohexyl, 4-ethylcyclohexyl, cycloheptyl,
norbornyl, and methylcyclohexyl radicals.
[0180] Examples of halogen-substituted C.sub.1-C.sub.20 alkyl
radicals are alkyl radicals substituted by fluorine, chlorine,
bromine, and iodine atoms, such as the 3,3,3-trifluoro-n-propyl
radical, the 2,2,2,2',2',2'-hexafluoroisopropyl radical, and the
heptafluoroisopropyl radical.
[0181] Particularly preferred are the unsubstituted
C.sub.4-C.sub.12 alkyl radicals.
[0182] If the
(C.sub.1-C.sub.20)-alkyl-(C.sub.2-C.sub.3)-alkoxysilane (F) which
acts as priming impregnating agent is present in the
organopolysiloxane dispersion of the invention, it is preferably
included in amounts of 0.05 to 0.95%, based on the overall aqueous
preparation of the coating material. (F) is included preferably at
between 0.1 to 0.8 wt %, more preferably 0.1 to 0.5 wt %, in the
aqueous coating material.
[0183] A further subject of the invention are coatings produced by
using the aqueous coating materials of the invention.
[0184] The aqueous silicone resin dispersions of the invention are
suitable not only for impregnating porous substances, of the kind
employed, for example, in the electrical insulant sector (e.g.,
glass fabric, mica), but also as casting and embedding compounds.
On account of the mild curing conditions, the aqueous silicone
resin dispersions of the invention have advantages in particular in
processing together with temperature-sensitive components (e.g.,
electronic components, casting moulds).
[0185] The aqueous silicone resin dispersions of the invention may
also serve, furthermore, for manipulating further properties of
preparations comprising them, or of solid bodies or films obtained
from aqueous polyorganosiloxane dispersions of the invention, such
as, for example: [0186] controlling the electrical conductivity and
the electrical resistance, [0187] controlling the flow properties
of a preparation, [0188] controlling the gloss of a wet or cured
film or of an article, [0189] increasing the weathering resistance,
[0190] increasing the chemical resistance, [0191] increasing the
shade stability, [0192] reducing the propensity to chalking, [0193]
reducing or increasing the static and sliding friction on solid
bodies or films obtained from preparations comprising an aqueous
polyorganosiloxane dispersion of the invention, [0194] stabilizing
or destabilizing foam in the preparation comprising aqueous
polyorganosiloxane dispersions of the invention, [0195] improving
the adhesion of the preparation comprising an aqueous
polyorganosiloxane dispersion of the invention to substrates,
[0196] controlling the filler and pigment wetting and dispersing
behaviour, [0197] controlling the rheological properties of the
preparation comprising an aqueous polyorganosiloxane dispersion of
the invention, [0198] controlling the mechanical properties, such
as flexibility, scratch resistance, elasticity, extensibility,
bendability, tensile behaviour, resilience, hardness, density, tear
resistance, compression set, behaviour at different temperatures,
coefficient of expansion, abrasion resistance, and also further
properties such as the thermal conductivity, combustibility, gas
permeability, resistance to water vapour, hot air, chemicals,
weathering, and radiation, and sterilizability, of solid bodies or
films obtainable from preparations comprising an aqueous
polyorganosiloxane dispersion of the invention, [0199] controlling
the electrical properties, such as breakdown strength, creep
resistance, arc resistance, surface resistance, specific breakdown
resistance, flexibility, scratch resistance, elasticity,
extensibility, bendability, tensile behaviour, resilience,
hardness, density, tear resistance, compression set, behaviour at
different temperatures of solid bodies or films obtainable from the
preparation comprising aqueous polyorganosiloxane dispersions of
the invention.
[0200] Examples of applications in which the aqueous silicone resin
dispersions of the invention can be used in order to manipulate the
properties identified above are the production of coating materials
and impregnations and of coatings and coverings obtainable
therefrom on substrates, such as metal, glass, wood, mineral
substrate, synthetic fibres and natural fibres for producing
textiles, carpets, floor coverings, or other products producible
from fibres, leather, plastics such as films, mouldings. With
appropriate selection of the preparation components, the aqueous
silicone resin dispersions of the invention may be further employed
in preparations as additives for defoaming, promoting flow,
hydrophobizing, hydrophilizing, dispersing of filler and pigment,
wetting of filler and pigment, substrate wetting, promotion of
surface smoothness, reduction of static and sliding friction on the
surface of the fully cured material obtainable from the additized
preparation. The aqueous silicone resin dispersions of the
invention can be incorporated in liquid form or in fully cured
solid form into elastomer materials. In this context they can be
used for reinforcing or for improving other service properties such
as the control of transparency, heat resistance, yellowing
propensity, and weathering resistance.
EXAMPLES
[0201] In the examples which follow, all parts and percentages
data, unless otherwise indicated, relate to weight. Unless
otherwise indicated, the examples below are carried out under the
pressure of the surrounding atmosphere, in other words
approximately at 1013 mbar, and at room temperature, in other words
at approximately 25.degree. C., or at a temperature which comes
about when the reactants are combined at room temperature without
additional heating or cooling. All viscosity data given in the
examples relate to a temperature of 25.degree. C. The solids
content of the emulsions identifies the sum total of all components
apart from water. Me denotes a methyl radical (--CH.sub.3). Ph
denotes a phenyl radical (--C.sub.6H.sub.5). Et denotes an ethyl
radical (--CH.sub.2--CH.sub.3). .sup.iOct denotes an isooctyl
radical=2,2,4-trimethylpentyl radical. "I." denotes inventive and
"N.I." denotes noninventive.
Example 1: Production of an Inventive and of a Noninventive Aqueous
Silicone Resin Dispersion
[0202] Using the components set out in tabular form below, an
inventive silicone resin dispersion is made in analogy to the prior
art, as described in EP1583790B1, and also a noninventive
dispersion. The quantities employed are reported in Table 1.
TABLE-US-00001 TABLE 1 Chemical identity/ Components manufacturer
I. N.I. Arlypon IT 5 Polyoxyethylene (5) 5.64 g 5.64 g isotridecyl
ether (nonionic emulsifier, manufacturer Cognis GmbH, Illertissen)
Arlypon IT 10 Polyoxyethylene (10) 7.08 g 7.08 g isotridecyl ether
(nonionic emulsifier, manufacturer Cognis GmbH, Illertissen) Water
12.18 + 12.18 + 100.14 g 100.14 g Aminosilicone 50 weight percent
2.85 g 2.85 g oil emulsion aqueous dispersion of a
polydiorganosiloxane, 99.3% of whose organic groups are methyl
groups and 0.7% of whose organic groups are N-(2-aminoethyl)-3-
amino-n-propyl groups and whose viscosity at 25.degree. C. is 450
mm.sup.2/s N.I. Silicone 1. Silicone resin 1, 0.0 g 171.0 resin
consisting of 90 mol % preparation MeSiO.sub.3/2 units (= T
possessing units) and 10 mol % only one kind Me.sub.2SiO.sub.2/2
units, with of repeating 8 mol % of EtO radicals units of the and 2
mol % of silicon- formula (1) bonded HO radicals and no being
distributed over mixture of at the T and D units, least two thereby
giving the such units meaning of R.sup.7, and having 2. Silicone
resin 2, different consisting of 100% of hydrocarbon MeSiO.sub.3/2
units (= T substituents: units), with 20 mol % of EtO radicals
being distributed randomly over the T units of silicone resin 2,
there being 80 percent by weight of silicone resin 1 and 20 percent
by weight of silicone resin 2 in the mixture, and 3. Calculated on
the mass of silicone resin 1, 10% by weight of triethoxyisooctyl
silane, the siloxane-silane preparation being in dispersion in
water and the fraction thereof in 100% of the dispersion being 50
percent by weight I. Silicone Silicone resin composed 171.00 g 0.0
g resin of 90 mol % MeSiO.sub.3/2 units and 10 mol %
.sup.iOctSiO.sub.3/2 units, with 18 mol % of EtO radicals and 1 mol
% of HO radicals being distributed randomly over these T units
Konservierer 10% solution of 2- 0.15 g 0.15 g MIT 10
methyl-4-isothiazolin- 3-one in water (preservative, manufacturer
Rohm and Haas) PARMETOL Mixture of 5-chloro-2- 0.72 g 0.72 g A 28 S
methyl-2H-isothiazol-3- one (CAS 26172-55-4) and 2-methyl-2H-
isothiazol-3-one (CAS 2682-20-4) (Preservative, manufacturer
Schulke & Mayr GmbH, Norderstedt) Triethanol- Triethanolamine
0.24 g 0.24 g amine
Example 2: Inventive and Noninventive Architectural Preservative
Coating with Supercritical Pigment Volume Concentration (PVC)
[0203] The following components were combined by mixing using a
high-speed Rotor Stator mixer of customary commercial form, to give
an inventive and a noninventive architectural preservative coating.
The quantities employed are reported in Table 2.
TABLE-US-00002 TABLE 2 I. N.I. Quantities Quantities Component in g
in g Water 310 310 In-can preservative 2.0 2.0 Film preservative
10.0 10.0 Cellulose thickener 3.0 3.0 PU thickener 2.0 2.0
Polyphosphate, sodium salt 2.0 2.0 Polyacrylate, sodium salt 2.0
2.0 Silicone antifoam 3.0 3.0 Titanium dioxide pigment 120.0 120.0
Silicatic filler 80.0 80.0 Talc 40.0 40.0 Calcium carbonate 215.0
215.0 Matting filler 12.0 12.0 Sodium hydroxide solution, 10% 1.0
1.0 Film-forming assistant 10.0 10.0 I. aqueous silicone resin 83.0
0 preparation as per Example 1 N.I. aqueous silicone resin 0 83.0
preparation as per Example 1 Styrene acrylate dispersion, 50% in
95.0 95.0 water, with a styrene to butyl acrylate ratio such as to
produce a minimum film-forming temperature of 15.degree. C. for the
polymer Total: 990 990
[0204] The formula results in an inventive and a noninventive
porous coating, since the pigment volume concentration (PVC)
thereof is above the critical PVC.
Example 3: Performance Tests of the Inventive and of the
Noninventive Construction Coating from Example 2
[0205] Testing of the construction coatings from Examples 2 for
their service properties, in accordance with the standard
specifications listed in Table 3:
TABLE-US-00003 TABLE 3 Test standard Unconditioned water
permeability rate (w.sub.24 Measurement to ISO in
kg/m.sup.2h.sup.0.5) 1062-3 but without prior conditioning Water
permeability rate (w.sub.24 in kg/m.sup.2h.sup.0.5) ISO 1062-3
Scrub resistance after conditioning: Measurement to DIN storage for
4 d under standard conditions of 53778-2 23.degree. C. and 50%
relative humidity Scrub resistance after 200 h QUV-B Measurement to
DIN weathering 53778-2 Surface hydrophobicity through beading
In-house testing effect protocol
Procedure for Determining the Surface Hydrophobicity:
[0206] One droplet of water (volume 1 ml) is applied from a pipette
to the surface under test. After 10 minutes, visual examination
evaluates how effectively the droplet wets the surface.
Evaluation System:
[0207] 1=substrate is not wetted, and water droplet beads off
completely and without residue from an inclined surface (slope
30.degree. relative to the plane)
[0208] 2=good beading effect but individual small droplets of water
remain hanging on the surface
[0209] 3=substrate is partly wetted, with water droplet beading off
incompletely
[0210] 4=substrate is wetted, and the water droplet no longer beads
off
[0211] 5=substrate is wetted, and the water droplet spreads
[0212] The results obtained are set out in Table 4.
TABLE-US-00004 TABLE 4 I. N. I. Construction Coating from coating
from Example 2 Example 2 Uncond. w.sub.24 in kg/m.sup.2h.sup.0.5
0.23 0.07 w.sub.24 in kg/m.sup.2h.sup.0.5 0.09 0.06 Scrub
resistance after 8600 >10 000 conditioning Scrub resistance
after QUV-B >10 000 >10 000 Surface hydrophobicity 1 4
[0213] When using the aqueous silicone resin dispersion of the
invention, it is observed that the water permeability rate is very
low even without conditioning. This low rate is maintained after
conditioning. The scrub resistance of the paint comprising the
aqueous silicone resin dispersion of the invention is already at
the highest level defined by the specified standard after simple
conditioning. This level is maintained after weathering. The most
conspicuous effect brought about by the aqueous silicone resin
dispersion of the invention is the surprising and new combination
of low water permeability in conjunction with low surface
hydrophobicity. Since the paint formulations consist of the same
components in the same proportions, this effect can be explained
only by the difference in behaviour between the inventive and the
noninventive silicone resin dispersion.
Example 4: Production of an Inventive and of a Noninventive Aqueous
Silicone Resin Dispersion
[0214] An inventive silicone resin dispersion is manufactured in
analogy to the noninventive dispersion in accordance with the
prior-art description in EP1583790B1, from the constituents listed
in tabular form below. The quantities employed are reported in
Table 5.
TABLE-US-00005 TABLE 5 Chemical identity/ Components manufacturer
I. N.I. Arlypon IT 16 Polyoxyethylene (16) 6.0 g 6.0 g (80% aqueous
isotridecyl ether solution) (nonionic emulsifier, manufacturer
Cognis GmbH, Illertissen) Water 3.5 + 3.5 + 38.24 g 38.24 g E.
Silicone Silicone resin 52.0 g 0.0 g resin composed of 95 mol %
MeSiO.sub.3/2 units and 5 mol % PhSiO.sub.3/2 units, with 17 mol %
of EtO radicals and 1.6 mol % of HO radicals distributed randomly
over these T units N.I. Silicone 1. Silicone resin 1, 0.0 g 52.0 g
resin consisting of 90 mol % MeSiO.sub.3/2 units (= T units) and 10
mol % Me.sub.2SiO.sub.2/2 units, with 8 mol % of EtO radicals and 2
mol % of silicon-bonded HO radicals being distributed over the T
and D units, thereby giving the meaning of R.sup.7, and 2. Silicone
resin 2, consisting of 100% of MeSiO.sub.3/2 units (= T units),
with 20 mol % of EtO radicals being distributed randomly over the T
units of silicone resin 2, there being 80 percent by weight of
silicone resin 1 and 20 percent by weight of silicone resin 2 in
the mixture, and 3. Calculated on the mass of silicone resin 1, 10%
by weight of triethoxyisooctyl silane, the siloxane-silane
preparation being in dispersion in water and the fraction thereof
in 100% of the dispersion being 50 percent by weight Konservierer
10% solution of 2- 0.1 g 0.1 g MIT 10 methyl-4- isothiazolin-3-one
in water (preservative, manufacturer Rohm and Haas) PREVENTOL
.RTM.BIT 10 10% strength alkaline 0.1 g 0.1 g solution of 1,2-
benzisothiazolin-3- one (preservative, manufacturer LANXESS)
Triethanolamine Triethanolamine 0.06 g 0.06 g
Example 5: Inventive and Noninventive Construction Coating Using
the Inventive and the Noninventive Aqueous Silicone Resin
Dispersions from Example 4
[0215] The following components were combined by mixing using a
high-speed Rotor Stator mixer of customary commercial form, to give
an inventive and a noninventive architectural preservative coating
(aqueous coating material). The quantities employed are reported in
Table 6.
TABLE-US-00006 TABLE 6 I. N.I. Quantity Quantity Component [g] [g]
Water 353.9 353.9 In-can preservative 2.0 2.0 Film preservative
10.0 10.0 Cellulose thickener 3.0 3.0 PU thickener 2.0 2.0
Polyphosphate, sodium salt 2.0 2.0 Polyacrylate, sodium salt 2.0
2.0 Silicone antifoam 4.0 4.0 Titanium dioxide pigment 117.0 117.0
Silicatic filler 78.0 78.0 Talc 39.0 39.0 Calcium carbonate 209.5
209.5 Matting filler 11.5 11.5 Sodium hydroxide solution, 10% 1.1
1.1 Inventive aqueous silicone resin 40.0 0.0 preparation as per
Example 4 Noninventive aqueous silicone resin 0.0 40.0 dispersion
as per Example 4 Vinyl acetate-ethylene copolymer 125.0 125.0
dispersion, 60% in water Total: 1000 1000
[0216] The formula results in an inventive and a noninventive
porous coating, since the pigment volume concentration (PVC)
thereof is above the critical PVC.
Example 6: Performance Tests of the Inventive and of the
Noninventive Construction Coating from Example 5
[0217] The testing of the construction coatings from Examples 5 for
their service properties takes place in analogy to Example 3.
[0218] The results obtained are shown in Table 7.
TABLE-US-00007 TABLE 7 N. I. I. Construction Coating from coating
from Example 5 Example 5 Uncond. w.sub.24 in kg/m.sup.2h.sup.0.5
0.72 0.25 w.sub.24 in kg/m.sup.2h.sup.0.5 0.17 0.15 Scrub
resistance after 8456 >10,000 conditioning Scrub resistance
after QUV-B >10,000 >10,000 Surface hydrophobicity 1 5
[0219] When using the aqueous silicone resin dispersion of the
invention, it is observed that the water permeability rate is much
lower even without conditioning than in the case of the comparable
noninventive construction coating. This low rate is maintained
after conditioning. The scrub resistance of the paint comprising
the aqueous silicone resin dispersion of the invention is already
at the highest level defined by the specified standard after simple
conditioning. This level is maintained after weathering. The most
conspicuous effect brought about by the aqueous silicone resin
dispersion of the invention is the surprising and new combination
of low water permeability in conjunction with low surface
hydrophobicity. Since the paint formulations consist of the same
components in the same proportions, this effect can be explained
only by the difference in behaviour between the inventive and the
noninventive silicone resin dispersion.
* * * * *